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Author: Subject: erythritol tetranitrate recrystallization
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[*] posted on 22-1-2014 at 01:07


I dissolved damp ETN in acetone with some NaHCO3.
Once dissolved .... It was filtered, diluted with some NaHCO3 and urea solution in water.
And then to drop ETN out of solution .... I simply leave the dish at 40-45*C and stirring to evaporate the Acetone.
I end up with ETN slush in water.




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[*] posted on 22-1-2014 at 07:56


why not just dump it in a large surface glass pan to evaporate near a window? acetone has a quite low boiling point and evaporates very quickly
it can be made to evaporate even faster if you suck all the water out of the ETN first by folding filter or cloth in half, thereafter applying tissue paper or similar to suck out water

however, isnt it hard / near impossible to dissolve NaHCO3 in acetone?




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[*] posted on 22-1-2014 at 10:29


There is enough water in the acetone (~5%) and my damp ETN to keep some dissolved. Majority of it isn't dissolved. But definitely produces fizzing.
The only reason I evaporate acetone in water is to keep water soluble inpurities out of my ETN. Also the crystals form much slower and are denser.




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[*] posted on 22-1-2014 at 16:22


I just dissolve my ETN in acetone, filter it with a coffe filter, and trop it into a small bucket of water. I just then filter it again and it is done!!
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[*] posted on 23-1-2014 at 08:06


I'm not sure that's such a good way to purify it underground. The idea behind recrystallization is that the slowly forming crystals will exclude everything else. The crystals are purer than the solution. When you pour it directly into water, the crystals form so quickly they might encase all the impurities again.
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[*] posted on 23-1-2014 at 12:53


nah, dornier.. its so dilute that it basically wont matter, however for absolutely safetly recrystallizing it in water with abit of NH4OH would be the best way to do it
EtOH dissolved ETN dumped in water to be recrystallized is seen as being perfectly pure, however im very worried about having caustic NaHCO3 with the ETN, why not use NH4OH??




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[*] posted on 23-1-2014 at 21:50


The Bicarbonate gives me a visual indicator and doesn't smell.
If I were to use NH4OH to neutralize the ETN .... Then there is a possibility of acidic (NH4)2SO4 to be trapped with the ETN.. Lol




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[*] posted on 24-1-2014 at 13:44


question is... would it be better to have acidic or basic stuck in it??
Na2SO4 would be acidic anyways wouldnt it?
the best for purity would be ethanol recrystallization, but 50 mL acetone can dissolve probably even more than 10g ETN where 200 mL hot ethanol will dissolve 10g ETN




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[*] posted on 24-1-2014 at 15:29


Ethanol is very expensive for me and hard to come by.
That's why I use acetone.
Na2SO4 is a neutral salt




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[*] posted on 27-1-2014 at 10:09


Invest in a decent fractionating distillation setup and have your own supply of EtOH.....that's the way I do it. No problems with solvent shortage, not to mention the endless supply for creating all kinds of barbaric herbal infusions for oral intake ;)



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[*] posted on 25-5-2014 at 17:36


i nitrated about 9.5 grams of erythritol this morning. using 30 ml of >90% nitric acid (distilled last weekend) in 60 ml of 98% sulfuric acid cooled in ice bath and slow addition of the erythritol. i let the reaction proceed for 40 minutes keeping temp between 10C and 20C. after the 40 minutes i let the mixture slowly heat up until NOx fumes began to appear. when the reaction mixture reached about 58C i cooled the beaker and then crashed.

the etn was already formed and the increased temp fused the mass of crystals as it cooled in water. broke up the mass, neutralized with conc. NaHCO3 and dried. crushed the slightly yellowish mass into powder, neutralized again and dissolved in the minimum amount of methanol. heating over a hot water bath, i reduced the solution beyond the saturation point, and, disturbing the liquid, it became a thick slush of etn crystals slightly wet with methanol. i emptied this mass into a buchner funnel, washed again with a final 15 ml portion of water and dried with vacuum filtration. all traces of yellow are gone. final product is snow white and like corn starch in consistency.

final mass weighed in at 10.4 grams not including the portions removed for testing and losses from cleaning and recrystallization.

a 100 mg mass pressed tightly into heavy foil confinement detonates with great force on heating. ears rang for 15 minutes...
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[*] posted on 25-5-2014 at 22:42


Quote: Originally posted by Rogeryermaw  
i nitrated about 9.5 grams of erythritol this morning. using 30 ml of >90% nitric acid (distilled last weekend) in 60 ml of 98% sulfuric acid cooled in ice bath and slow addition of the erythritol. i let the reaction proceed for 40 minutes keeping temp between 10C and 20C. after the 40 minutes i let the mixture slowly heat up until NOx fumes began to appear. when the reaction mixture reached about 58C i cooled the beaker and then crashed.

the etn was already formed and the increased temp fused the mass of crystals as it cooled in water. broke up the mass, neutralized with conc. NaHCO3 and dried. crushed the slightly yellowish mass into powder, neutralized again and dissolved in the minimum amount of methanol. heating over a hot water bath, i reduced the solution beyond the saturation point, and, disturbing the liquid, it became a thick slush of etn crystals slightly wet with methanol. i emptied this mass into a buchner funnel, washed again with a final 15 ml portion of water and dried with vacuum filtration. all traces of yellow are gone. final product is snow white and like corn starch in consistency.

final mass weighed in at 10.4 grams not including the portions removed for testing and losses from cleaning and recrystallization.

a 100 mg mass pressed tightly into heavy foil confinement detonates with great force on heating. ears rang for 15 minutes...


Could you elaborate on the purpose of heating up the nitrator contents to 58C? This seems awful high and a very possibly dangerous region of temperature for this type of reaction. As you described yourself the mass had fused together due to the temperature being close to the melting point of the product.
Also as a side note...the use of highly concentrated nitric acid is not a must in ETN mixed acid nitration. The regular 68% azeotrope will do just fine and give a similar yield.




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[*] posted on 25-5-2014 at 23:03


ah but i had conc. HNO3 on hand and do not have lab grade at my disposal. i prefer to use it as is instead of diluting it. adding water to nitric that strong is exothermic and causes some degradation of the acid.

i allowed the mixture to heat up because of some failed nitrations in the past. dousing too early or running the reaction at too low a temperature has (in my experience) caused a lot of lower nitrated products and incomplete reactions. as a safety measure, i always keep a bucket of ice water handy directly below my reaction vessel. if things get out of hand or i can't cool the reaction fast enough, a quick swat will dump the entire mess into ice water, quenching things immediately. that measure has saved me more than once.
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[*] posted on 25-5-2014 at 23:30


Ah, I see...the causes for things always tend to be unnervingly trivial :D Since you have highly concentrated nitric at hand, why not use a nitric acid only route for obtaining of ETN and skip the sulfuric component entirely. I trust it will give a far superior yield similar to the case with PETN. Also I would advise against repeating the high temperature synthesis method that you practiced....there must be a better way to obtain a decent yield with mixed acid method if you choose to use this one. A different ratio of acids is a starting point. Perhaps the failed syntheses from the past were due to using too concentrated acids? With PETN nitration there is an established undestanding that a certain amount of water in the nitration mix is essential to the reaction mechanism and without it (in case of highly concentrated acids) the reaction rate drops dramatically.

Please find the articles attached:


Attachment: ETN Paper accepted PEP.pdf (806kB)
This file has been downloaded 555 times

Attachment: Nitration of pentaerythritol by HNO3-H2SO4-H2O system .pdf (1.2MB)
This file has been downloaded 476 times




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[*] posted on 26-5-2014 at 08:03




<1 gram initiated by 3 mg lead styphnate fired electrically.

[Edited on 26-5-2014 by Rogeryermaw]
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[*] posted on 26-5-2014 at 08:09


Quote: Originally posted by Rogeryermaw  
ah but i had conc. HNO3 on hand and do not have lab grade at my disposal. i prefer to use it as is instead of diluting it.

I assume by "conc." you mean fuming, and by "lab grade" you mean conc.? (Conc. = ~68%, fuming =>86%.)




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[*] posted on 26-5-2014 at 08:15


geez...could that have been of worse quality? i'll work on a better one today.

yes you assume correctly, zyklon.

you can hear in the background, my son enjoyed the demonstration.

[Edited on 26-5-2014 by Rogeryermaw]
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[*] posted on 26-5-2014 at 13:49


5 gram charge primed with 500 mg 50/50 etn w/ lead styphnate. better quality anyway...

ya i'm barefoot..what?



[Edited on 26-5-2014 by Rogeryermaw]
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[*] posted on 13-12-2015 at 16:53


I have been experimenting with recrystallizing ETN with 91 percent isopropyl alcohol. My goal it's to get very low density crystals. I bring the alcohol up to 58c and start adding the ETN and stir it in. Once all is dissolved I dump into about a gallon of ice water which is swirling when the ETN solution is poured in.

This leaves a very nice clear crystal with platlet shape. Unfortunately the crystals are to dense to be set off by my spark gap detonator.

I follow the same steps with denatured alcohol and it produces a fine light powder that does work with the spark gap.

Why does the isopropyl give a Different structure form the denatured? Is there a way to get lighter finer crystals using isopropyl? I want to use it because it's half the cost of denatured.
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[*] posted on 14-12-2015 at 12:22


I can think of some possible solutions involving more complicated apparatus, but a simple immediate solution might be to use smaller volumes (break it into batches) and ensure the dilution is as fast as possible with extremely vigorous stirring. I am assuming that greater stirring/agitation and faster dilution would be beneficial here.



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[*] posted on 14-12-2015 at 14:23


Henning,

The batch is small. 300ml of ETN solution into a gallon of ice water. I can use a mixer to better agitate the ice water while pouring.
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[*] posted on 16-8-2020 at 20:37


Using 50 mL of acetone, I dissolved what I estimate to be 22 ish grams of dry ETN. The ETN was still wet after vacuum filtering when dissolved in the acetone and I made the mistake of not weighing it. I would estimate it was at least 30 grams of material including water. Can anyone explain what this separation is? Maybe the ETN saturated acetone separates from the water? I do not see how there could have been 50 mL of water in my vacuum dried ETN.

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[*] posted on 17-8-2020 at 01:38


Quote: Originally posted by Brightthermite  
Using 50 mL of acetone, I dissolved what I estimate to be 22 ish grams of dry ETN. The ETN was still wet after vacuum filtering when dissolved in the acetone and I made the mistake of not weighing it. I would estimate it was at least 30 grams of material including water. Can anyone explain what this separation is? Maybe the ETN saturated acetone separates from the water? I do not see how there could have been 50 mL of water in my vacuum dried ETN.



You have added 50 ml of acetone to 22 g of ETN, how do you have a total volume of over 100 ml? Was anything else added? 50 ml of acetone plus 30 g of wet ETN should be less than 80 ml in volume.....

Edit - maybe you had 60 g of wet ETN?

[Edited on 17-8-2020 by B(a)P]
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[*] posted on 17-8-2020 at 11:37


Quote: Originally posted by B(a)P  
Quote: Originally posted by Brightthermite  
Using 50 mL of acetone, I dissolved what I estimate to be 22 ish grams of dry ETN. The ETN was still wet after vacuum filtering when dissolved in the acetone and I made the mistake of not weighing it. I would estimate it was at least 30 grams of material including water. Can anyone explain what this separation is? Maybe the ETN saturated acetone separates from the water? I do not see how there could have been 50 mL of water in my vacuum dried ETN.



You have added 50 ml of acetone to 22 g of ETN, how do you have a total volume of over 100 ml? Was anything else added? 50 ml of acetone plus 30 g of wet ETN should be less than 80 ml in volume.....

Edit - maybe you had 60 g of wet ETN?

[Edited on 17-8-2020 by B(a)P]


I guess there was much more water in it then I estimated. Still though that is a huge volume change. Interestingly enough I decided not to crash in water and just dumped the solution into a dish to evaporate. It evaporated very fast and only left the ETN damp with water. Acetone and water azeotrope evaporated most of the water away?
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[*] posted on 23-8-2020 at 03:30


I've used methanol everytime. Yield is sometimes off by a lot. Not sure why and sometimes it forms bubbled up hollow spheres than crystals. Not sure why.


Also a nice tip I discovered which may be a little risky is to dump your ETN in the acid mix into a smaller amount of water all at once with no stirring initially. It favors larger crystal size which filters wayyyy faster and makes it less likely for the filter paper to be eaten apart due to being in contact with acids for a long time. After that wash with lots of baking soda solution and recrystallize with a pinch of baking soda into the solvent. Make sure to stir and try to get rid of as much trapped acids as possible. Stabilize with baking soda and urea.
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